Reducing the caking of nitrogencontaining salts



United States Patent 3,201,354 REDUCING THE CARING (BF NITRGGEN- (IQNTAINENG SALTS Joseph E. Wilson, .l'ohn C. Hillyer, and Van C. Vives,

Bartlesville, Okla, assiguors to Phillips Petroleum Company, a corporation of Delaware No Drawing. Original appiication Aug. 18, 1960, Ser. No. 50,312, new Patent No. 3,116,185, dated Dec. 31, 1.963. Divided and this application Mar. 25, 1963, Ser. No. 267,805

'1 Claims. (Cl. 252-383) This application is a divisional application of our Patent No. 3,116,185, filed August 18, 1960, and issued December 31, 1963.

This invention relates to reducing the caking tendency of nitrogen-containing salts. In another aspect, it relates to the production of treated, non-caking nitrogen-containing salts, such as ammonium nitrate, these treated salts being valuable as free-flowing fertilizer with little or no tendency to cake on standing. In another aspect, it relates to nitrogen-containing salts, such as ammonium nitrate, treated to reduce their normal tendency to cake on standing, and to explosive compositions containing such treated salts. In a further aspect, it relates to a novel two-component anti-caking agent, useful in treating such salts, and to a method of preparing such anti-caking agent.

Many nitrogen-containing salts or compounds in powder, crystalline, or granular form have a normal tendency to cake or become sticky on standing and form hard masses. This caking is usually promoted by changes in humidity, temperature, and/ or pressure, and occurs under conditions during storing, shipping, and handling.

The tendency of these salts to cake on standing presents difficulties in the handling and use of such salts. For example, where such nitrogen-containing salts are used as fertilizers, this caking tendency impairs the drillability of the fertilizer and increases the effort and cost of uniformly distributing the fertilizer in the field because caked fertilizer causes clogging of distribution machinery and other handling problems. Similarly, where nitrogen-containing salts, such as ammonium nitrate, are used as ingredients in explosive compositions, the caking tendency of such salts adversely affects the sensitivity of the explosive composition, and may render it incapable of satisfactory detonation.

Many methods have been proposed, used or patented in the past for overcoming, reducing, or preventing the normal tendency of such nitrogen-containing salts to cake on standing, including treatment of such salts with various anti-caking, conditioning, or partition agents. While some of these methods and prior art anti-caking agents have been satisfactory in providing some measure of reduced caking, others have proven unsatisfactory because they involve or necessitate complex methods of treatment, or involve the use of large amounts of anti-caking agent which adds to the expense of application. In fact, large amounts of anti-caking agent reduce the nitrogen content of the treated salts and make such treated salt economically unattractive to a farmer who is interested in getting as much plant nutrient value as possible out of the nitrogen-containing salt he buys for use as a fertilizer.

Accordingly, an object of this invention is to reduce the caking of nitrogen-containing salts. Another object is to provide an improved method of treating nitrogen- 3,21,354- Patented Aug. 17, 1.935

containing salts, such as ammonium nitrate, to reduce their normal tendency to cake on standing. Another object is to produce treated non-caking nitrogen-containing salts, such as ammonium nitrate, which salts are valuable as free-flowing fertilizers with little or no tendency to cake on standing. Another object is to provide improved explosive compositions containing non-caking nitrogencontaining salts, which explosive compositions are characterized by satisfactory sensitizing and detonation properties. A further object is to provide a novel anti-caking agent, and a novel method of preparing the same. Further objects and advantages of this invention will become apparent to those skilled in the art from the following discussion and appended claims.

We have now discovered that the normal tendency of particulate nitrogen-containing salts, such as ammonium nitrate, to cake on standing can be reduced or prevented by treating such salts with a novel anti-cakin'g agent comprising a major amount of kaolin and a minor amount of an alkali metal salt of an alkylaryl sulfonic acid, said anti-caking agent hereinafter occasionally referred to as the novel two-component anti-caking agent of this invention.

Kaolin, used as a major component of the anti-caking agent of this invention, is a clay whose essential constituent is the mineral kaolinite, a hydrated aluminum silicate. Kaolin is sold as an article of commerce under various trade names, such as Paragon clay, Suprex clay, Barden clay and Barnet clay; a specification of the latter type, having a standard U.S. sieve mesh size of 98% through a 325 mesh screen, is given in Table I. Suprex, Barden, and Barnet clays are all beta-axis disordered, while Paragon is not.

The loss on ignition is essentially all chemically combined water.

The alkylaryl sulfonates, employed in a minor amount as the other essential component of the novel anti-caking agents of this invention, are water-soluble alkali metal salts of alkylaryl 'sulfonic acids which have a total of 7 to 30, preferably 10 to 20, carbon atoms per molecule with preferably 1-4 of these carbon atoms in each of the aliphatic hydrocarbon chains. The aryl portion of these compounds can be either benzene or naphthalene nucleus. These sulfonates can be prepared by the well-known procedure of sulfonating the corresponding alkyl aromatic compound and forming the alkali metal salt of the resulting sulfonic acid.

Representative alkyaryl sulfonates useful in the practice of this invention include the sodium salt of Z-n-butylbenzenesulfonic acid; the sodium salt of 3-tert-dodecylbenzenesulfonic acid; the potassium salt of 4-n-eicosylbenzcnesulfonic acid; the potassium salt of 4-n-tetradecylbenzenesulfonic acid; the lithium salt of 4-tetracosylbenzenesulfonic acid; the disodium salt of G-n-decylbenzenep-disulfonic acid; the disodium salt of dimethylnaphthalene-l,2-disulfonic acid; the trirubidium salt of 5-terthexadecylbenzene-2,4,6-trisulfonic acid; the sodium salt of methylnaphthalenesulfonic acid, such as the sodium salts of 1-methylnaphthalene-Z-sulfonic acid, l-rnethylnaphthalenel-sulfonic acid, and mixtures thereof; the sodium salt of o-n-eicosylnaphthalene-l-sulfonic acid; the trisodium salt of 6,7,8-triethylnaphthalene-1,2,3-trisulfonic acid; the dicesium salt of 2,5-dimethylbenzene-1,3-disultonic acid; the disodium salt of 4,6-di-n-decylnaphthalene- 1,8-disulfonic acid; the potassium salt of 7-tert-dodecylnaphthalene-Z-sulfonic acid; the sodium salt of 2,5-dimethylbenzenesulfonic acid; and the like, including mixtures thereof. Of these respective sulfonates, the sodium salts of methylnaphthalenesulfonic acid and dimethylnaphthalenesuifonic acid are preferred, such materials being commercially available.

Both of the components of the novel anti-caking agent of this invention are solids and are inert with respect to the nitrogen-containing salts themselves. The sulfonates are water soluble compounds which may be used in particulate form in treating the nitrogen-containing salts, or applied as an aqueous solution, for example a 5 to 75 weight percent aqueous solution, preferably about a 50 weight percent aqueous solution. Said sulfonates are also characterized by the fact that they are not dyestuffs.

The nitrogen-containing salts, in particulate form, are treated with an amount of the novel two-component anticaking agent of this invention suflicient to reduce the caking tendency of the nitrogen-containing salts. Generally, only a small amount of the anti-caking agent is necessary to provide adequate protection against caking, with amounts in the range of 0.5 to 5 weight percent of the treated nitrogen-containing salt being generally applicable. As mentioned hereinbefore, the kaolin component comprises a major amount of the anti-caking agent, while the sulfonate component comprises a minor portion of the anti-caking agent. Generally, for most applications, the amount of the sulfonate component in the anticaking agent will be a synergistic amount, usually within the range between 0.25 and 12 weight percent, preferably in the narrow range between 0.5 and 5 weight percent, of the anti-caking agent. Thus, when the anti-caking agent is applied to the nitrogen-containing salt, the amount of sulfonate component in the anti-caking coating can be exceedingly small, e.g., 0.01 Weight percent of the treated nitrogen-containing salt.

The novel anti-caking agent of this invention can be prepared by a variety of methods. For example, a water solution of the sulfonate can be sprayed onto the kaolin, or either of the latter can be slurried up in a solution of the sulfonate. In still another method, the kaolin can be dry-mixed with the sulfonate. In order to insure a homogeneous mixture of the two components, it is preferred to employ some method of violently agitating the mixture, such as a mill like a Waring Blendor in which knife blades shear the material together. Such mixing can be carried out with the aid of a small amount of water, although the kaolin itself may contain some combined water and free water. It is preferred to dry the kaolin to a maximum Water content of to 15 weight percent. The additional water can also be supplied by using an aqueous solution of the sulfonate and spraying such solution on the kaolin.

The kaolin can be dried before being admixed with the sulfonate, or the two-component mixture can be subsequently dried after mixture, or both methods of drying can be used. Whichever drying method is used, the final anti-caking product will normally contain from 0.5 to 8 weight percent water, preferably 1 to 4 weight percent water. This novel mixture is then applied to the particulate nitrogen-containin" salt by contacting the same therewith, for example by tumbling or other equivalent methods. Generally, the kaolin used will have a particle size liner than 200 mesh, preferably finer than 325 mesh, US. Standard Sieve. The treated or coated nitrogencontaining salt will generally have a moisture content not greater than 0.30 weight percent, preferably less than 0.20 weight percent. In most instances the treated nitrogencontaining salt can be subsequently dried further if necessary, or if desire We have surprisingly discovered that the treatment of the nitrogen-containing salt with the novel two-component anti-caking agent of this invention reduces the normal caking tendency of the nitrogen-containing salt to a much greater extent than when the nitrogen-containing salt is treated with either the sulfonate itself, or the kaolin itself. Further, we have surprisingly discovered that the combination of a very minor amount of said sulfonate with kaolin is a synergistic combination whose anti-caking characteristics exceed the sum of the anti-caking effect of the sulfonate and the kaolin used alone. The effect of the sulfonate on the anti-caking properties of the kaolin is over and above that predicted from the separate or joint anti-caking effect of the sulfonate and kaolin. We have further discovered that the amount of the novel anticaking agent of this invention necessary to satisfactorily reduce the caking tendency of the nitrogen-containing salt is comparatively low, with the result that the process of this invention is economically attractive in that the nitrogen content of the treated salt is not appreciably lowered and when such treated salts are used as fertilizer their plant nutrient value remains high. Also, we have discovered that because it only takes a small amount of the anti-caking agent of this invention to insure non-caking of the treated nitrogen-containing salts, the latter, especially treated ammonium nitrate, do not adversely affect the sensitivity of explosive compositions when such treated salts are employed as ingredients of such compositions.

As mentioned above, the alkylaryl sulfonates used in this invention are commercially available. One useful method of preparing such sulfonates is by the sulfonation of cycle oils, and neutralization of the resulting sulfenic acids with an alkali metal hydroxide. This particular method will now be discussed and presented as illustrative of a preferred method for preparing the alkali metal salts of the alkylarylsulfonic acids used in this invention.

Cycle oils which can be used to prepare the sulfonates include those from catalytic cracking units, which cycle oils have a boiling range within the range of from 375 to 700 F. at atmospheric pressure, and which generally contain from 20 to weight percent aromatics as determined by the silica gel adsorption method of ASTM D 936-55, such cyclo oils also including concentrates thereof which can be prepared by such means as solvent extraction with liquid S0 and the like. The sulfonation of the cycle oils can be carried out by contacting the same with a sulfonating agent at a temperature generally in the range of 0 to (3., usually between 25 and 75 C. Sulfonating agents which can be used include sulfuric acid, oleum, sulfur trioxide and other well-known sulfonating agents. The amount of sulfonating agent employed will vary and be dependent upon such things as the aromatic content of the cycle oil, but generally the sulfonating agent will be employed in amounts within the range of from 0.2 to 5.0 grams per gram of cycle oil.

After sulfonation, the sulfonation mixture can then be neutralized with an alkali metal oxide, hydroxide, or carbonate, preferably with an aqueous solution of the same having a concentration within the range from 10 to 50 weight percent. The amount of neutralizing agent employed will be that suflicient to effect neutralization and to insure the same an excess of the neutralizing agent will be employed. Generally, the amount of neutralizing agent used will be suflicient to provide from 1 to 2 moles of the same per mole of the sulfonating agent used in the sulfonation step.

Following neutralization of the sulfonic acids, the resulting alkali metal salts can be recovered :by any suitable process. Such sulfonates are preferably recovered by extracting the neutralization mixture with water, for example, 1 to grams of water per gram of cycle oil charged to the sul-fonation reaction. If desired, a suitable dilution step can be employed between the sulfonation and neutralization steps. If a large amount of water is employed in such a dilution step, it may not be necessary to add anyadditional water after neutralization. The resulting water soluble alkali metal salts of the alkylarylsulfonic acids can then be recovered from the aqueous solution by any suitable process. For example, the aqueous solution can be evaporated or the water removed by means of an azeotr ope with methyl alcohol or the like.

As mentioned hereinbefore, the treated nitrogen-containing salts of this invention, especially ammonium nitrate, are useful in explosive compositions where such salts are used in admixture with carbonaceous material. Generally, the explosive compositions of this invention will contain a major amount of the hereindescri bed treated nitrogen-containing salt as oxidizer, and a minor amount of carbonaceous material. Usually this will be in the range between 93 to 98 weight percent of the treated nitrogen-containing salt and 2 to 7 weight percent of the carbonaceous material. The carbonaceous material employed in preparing these novel explosive compositions include any of those proposed or used heretofore. In particular, the carbonaceous materials we prefer to employ are parafiinic hydrocarbons boiling in the range between 350 and 725 F., with an API gravity of from to 60, and a viscosity of to 140 SUS at 100 F. A specific carbonaceous material of this type is diesel fuel. Other known solid carbonaceous materials which can be employed include ground walnut hulls, asphalt, pitch, kerosene, coal tar, and the like. Liquid carbonaceous materials are preferred.

Although the subject invention is of particular value in treating ammonium nitrate, it should be understood that this invention is not limited thereto but includes treating any nitrogen-containing salt which normally tends to cake on standing. Such other salts representatively include sodium, potassium, and calcium nitrates, monoammonium sulfate, ammonium sulfate, urea, and the like, including mixtures thereof. These nitrogen-containing salts can be treated or coated according to this invention in particulate for, e.g., prills, grains, crystals, beads, etc. An example of a useful mesh size, of prilled ammonium nitrate, is between 8 and 14 mesh, U.S. Standard Sieve.

Although the novel two-component anti-caking agent of this invention when used by itself is sufiicient to satisfactorily reduce or prevent the normal caking tendency of nitrogen-containing salts treated therewith, it is also within the scope of this invention to utilize other known anti-caking agents in combination with the two-component agent of this invention.

Further objects and advantages of this invention will be apparent from the following examples; however, the

- subject invention is not to be unduly construed as limited by these examples or to the ingredients, amounts, temperatures, etc, expressed in these examples, since the same are set forth merely for illustrative purposes.

Example I Alkali metal alkylaryl sulfonates useful in the practice of this invention were prepared by a series of runs in which several different refinery streams which con-. tained aromatic hydrocarbons (primarily alkyl naphthalenes) were sulfonated and the resulting alkylaryl sulfonic acids neutralized to yield the corresponding sulfonates.

In these runs, an amount of the hydrocarbon to 'be sulfonated was charged to a B-necked, l-liter, round-bottomed flask which was fitted with a stirrer, a therometer and a dropping funnel. In each run, an amount of fuming sulfuric acid was charged to the flask by means of the dropping funnel, and an ice bath was employed to maintain the temperature of thereaction mixture between 17 and 20 C. during the acid addition. After all of the acid had been added, the ice bath was removed and an electric heating mantle was placed around the flask. The mixture was then heated to 6566 C. for 60-70 minutes while stirring, after which 300 grams of ice was added to the sulf-onation reaction mixture containing the alkylaryl sulfonic acids. An amount of aqueous sodium hydroxide solution was then added dropwise until the pH of the sulfonation mixture reached 8. During the addition of caustic, the temperature was maintained below 30 C. by means of an ice bath.

At the end of neutralization in each run, the oil layer was decanted ofi. Approximately one liter of methyl alcohol was then added to the water layer. The methyl alcohol-water solution was then heated to drive oif a methyl alcohol-water azeotrope, and the remaining dark slurry comprising sodium alkylaryl sulfonates was subjected to drying in a vacuum oven at 65 C. and and max imum vacuum of 15" Hg absolute.

Runs 1 and 2 were light cycle oils and that used in Run 3 was a light fraction of one of these cycle oils.

Light cycle oil #1 was obtained from a fluid catalytic cracking unit which was operated at a high recycle ratio, and this cycle oil had the following characteristics:

cracking unit and it had the following characteristics:

Distillation ASTM: F. IBP 424 10% 489 20 a 501 30 511 40 521 50 529 60 542 70 554 API gravityzSLG Calculated BMCI:43.7 Wt. percent aromatics by ASTM D 93655:25.2%

Light cycle oil #2A was a fore fraction of light cycle oil #2. This stream was fractionated at 50 mm. Hg absolute pressure. The fractionation data are as follows:

Fraction Head temp., F. Refractive index 1113 The first three fractions, representing 27.8 weight percent of the total cycle oil, were combined, sulfonated, and neutralized as described above.

The results of sulfonating and neutralizing the abovedescribed refinery streams are expressed below as Table H.

mercial press, and the pressure required to break each cake was recorded. The pressure in p.s.i. was then calculated and recorded. This cake-breeaking procedure is a modification of the test procedure described in Ind. & Eng. Chem, 33, 121-127 (1941). The results of these tests are expressed below as Table III.

X See Example I and Table II.

TABLE II Recovered from neutralized mixture, grams Fummg aq. Run No. Hydrocarbon stream Oil H280 NaOH Unsulto- Sodium nated oil NazSOl alkylaryl sulfonate Light cycle oil #1 100 150 300 27 135 135 Light cycle oil #2--- 400 150 300 295 144 145 Light cycle oil #2A 170 150 300 83 157 105 Example 11 The sulfonates prepared in Example I were evaluated as anti-caking agents for nitrogen-containing salts in the following manner.

In these runs, the sodium allsylaryl sulfonate was applied to a kaolin clay (Barnet clay) by contacting the clay with a by weight aqueous solution of the sulfonate. After the sulfonate had been applied to the clay, the treated clay (containing 3 wt. percent of said sulfonate) was then tumbled onto commercial ammonium nitrate prills. The tumbling time was approximately 10 minutes.

The moisture content of the treated ammonium nitrate prills was then determined, after which the treated nitrate was tested for caking by a test hereinafter referred to as the cake test.

In this test, 65 gram portions of the treated nitrate was poured into polyethylene cylinders fabricated from two layers of 1 /2 mil wall thickness polyethylene. The inside diameters of the cylinders were 1% inches, and the ends of the cylinders were plugged with Lucite blocks /2 inch thick. The blocks were held in the cylinders by means of cellophane tape. The loaded cylinders were then placed in a brass mold containing 3 holes, each 4 inches deep and 2 inches in diameter. A bellows was then attached to the top of the mold so as to supply 24 p.s.i. air pressure to the nitrate particles in the cylinders. The entire arrangement was then placed in an oven and maintained at 140 F. for 18 hours. The mold was then removed from the oven and opened, and the nitrate cakes which had been formed were removed from the cylinders. The cross-sectional area of each cake was 2.75 square inches. The cakes were then tested to breaking or crushing in a Carver com- The data of Table 111 show that treatment of the nitrogen-containing salt with the alkali metal alkylaryl .sulfonate-kaolin anti-caking agent of this invention completely prevented the normal tendency of said nitrogencontaining salt to cake on standing.

Example III A number of runs were carried out in which the sodium salt of methylnaphthalene sulf-onic acid was admixed with kaolin to prepare the novel anti-cak-ing agent of this invention, after which a particulate nitrogen-containing salt was contacted with said agent to reduce the normal tendency of said salt to cake on standing.

In each of these runs, a 50 wt. percent aqueous solution of said sulfonate was sprayed onto a kaolin clay in an amount sufficient to provide a sulfonate-kaolin mixture containing 3 weight percent of said sulfon-ate. Rapid agitation was employed to insure homogeneity, and the mixture was then dried. The dried two-component coating agent was then tumbled onto commercial ammonium nit-rate prills for approximately 10 minutes. The moisture content of the treated prills was then determined, after which the treated prills were evaluated according to the cake test described in Example II.

For purposes of comparison, similar runs were carried out in which ammonium nitrate prills were contacted individually with the sulfonate and kaolin. The treated prills of these runs were also evaluated by the cake test. For further purposes of comparison, untreated prills (control) were evaluated by the cake test.

The results of these runs and cake tests are set forth in Table IV.

TABLE IV Moisture Ave. crushing 7 Type of Amt. of content of strength of Run No. Coating agent kaolin 1 coating agent treated treated applied, wt. product, wt. product, percent percent psi.

1 None (control) 0. 18 383 2-- 0 0. 19 400 3 0 0.20 415 4 0 0. 21 435 5 0 0. 22 460 6 0 0. 23 485 7 0 0. 24 510 0 0.25 545 0 0.26 580 0 0. 27 615 0.03 0. 17 276 A 1 0. 08 A 1 0. 16 340 A 1 0. 22 500+ A 3 0. 22 500+ B 1 0. 08 20 B 1 0.17 120 B 1 o. 22 500+ B 3 0.22 500+ C 1 0. O8 155 C 1 0.25 600+ C 3 0. 08 110 C 3 0. 400 D 1 0.08 170 D 1 0.25 600+ D 3 0. 08 125 D 3 0. 25 600+ A 1 0. 10 0 A 1 0. 16 0 A 1 0. 20 0 B 1 0. 10 O B 1 0. 16 0 B 1 0. 20 0 C 1 0. 10 0 C 1 0. 21 0 D 1 0. 10 0 D 1 0.20 0

In this example, a kaolin (Barnet clay) was dry mixed with 3 wt. percent of the sulfonate of Example 111, and the mixture tumbled with ammonium nitrate prills. An amount of this kaolin was also mixed with 3 wt. percent of said sulfonate and sufiicient water to form a 50% slurry, which was dried, broken up, and similarly tumbled With ammonium nitrate pri'lls. These treated samples were evaluated by the cake test, and the result thereof, together with a control, are set forth in Table V.

TABLE V Amt. of Moisture Ave. crush- Method of coating content of ing strength Run No. preparing coating agent treated of treated agent applied, product, product,

wt. wt. p.s.i. percent percent 1 (control). 0 0. 22 460 2 Dry mixed 1 0.22 3 ed as slnrry-.. l 0.22 180 The data of Table V shows that alternative methods of preparing the novel two-component .anti-caking agents of this invention can be used, and that nitrogen-containing salts treated with such agents will efiectively reduce the normal caking tendency of such salts.

Example V The synergistic activity of the two-component anticaking agent of this invention is graphically demonstrated by the following example.

In each of a plurality of runs, 250 grams of prilled ammonium nitrate were tumbled with various treating ma- :terials for 10 minutes in a wide mouth quart bottle at a speed of 78 rpm. After treatment, 65 grams of the treated ammonium nit-rate sample were evaluated by the above-described cake test, the excess portion of the treated sample being used for moisture analyses. Triplicate runs were made with each treating material. For purposes of comparison, untreated ammonium nitrate samples were also evaluated in triplicate runs. Results of these evaluations are set forth m Table VI.

TABLE VI Amt. of Moisture Crushing Run Coating agent coating content of strength of No. agent coated coated applied, product product, p.s.i wt. percent wt. percent None (control) 0 0.14 480 do 0 0. 14 420 ave. 450

0 0.14 450 4 1 0.13 320 5 1 0.13 310 ave. 320 6 do 1 0. 13 330 7 Sulfonate b 1 0. 19 150 3 d0 1 0.19 ave.

1 0. 19 1 0. 13 0 1 0.13 0 ave. 0 1 0.13 0

B Barnet Clay.

b A commercial alkyluaphthalene sulfonate (Na salt) of this invention.

a Barnet Clay containing 2.9 wt. of same snlfonate used in Run Nos 7-9, the combination prepared by spraying a solution of the sulfonate on the kaolin.

Examination of the data of Table VI shows that the two-component combination anti-calcing agent of this invention (Run Nos. 1012) is truly synergistic in that its combined anti-caking effect exceeds the anti-caking eifect of the components (kaolin and sulfonate) used above =(Run Nos. 49).

Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and the foregoing discussion and examples should not be construed to unduly limit this invention.

We claim:

1. A novel anti-caking agent for preventing the caking tendency of nitrogen-containing compounds, said agent consisting essentially of an admixture of kaolin into which has been incorporated an alkali metal salt of an alkylaryl sulfonic acid, said salt being present in the amount of from 0.25 to 12 weight percent, based on the total weight of the ianti-caking agent, and having a total of 7-30 carbon atoms per molecule wherein the aryl portion of said molecule is selected from the group consisting of benzene and naphthalene.

2. A method of making an anti-caking agent which comprises the steps of mixing kaolin with an aqueous solution containing from 0.25 to 12 weight percent on a dry weight basis of said agent an alkali metal salt of an alkylaryl sulfonic acid having a total of from 7-30 carbon atoms per molecule wherein the aryl portion of said molecule is selected from the group consisting of benzene and naphthalene, and drying the resulting admixture to produce a compound capable of reducing the normal tendency of a particulate nitrogen-containing compound to cake on standing.

3. The anti-caking agent according to claim 1, wherein said salt is a sodium salt.

4. The anti-caking agent according to claim 1, wherein said salt is the sodium salt of methy-lnaphthalenesulfonic acid.

5. The anti-caking agent according to claim 1, wherein said salt is the sodium salt of dimethylnaphthalenesulfonic acid.

6. The method according to claim 2, wherein said salt is the sodium salt of rnethylnaphthalenesulfonic acid.

7. The method according to'clairn 2, wherein said salt is the sodium salt of dimethylnaphthalenesulfonic acid.

References Cited by the Examiner UNITED STATES PATENTS 2,782,096 2/57 Ames 23-103 3,014,783 12/6 1 Young 23- 103 3,632,450 5/62 Blackwell 149''7 3,034,858 -5/62 Vives 252383 XR 3,041,159 6/ 62 Smith 23103,XR 3,111,437 1 1/63 Hino et al. 14946 XR OTHER REFERENCES Condensed Chemical Dictionary, 4th Ed., Rose-Reinhold Pub. Co. (1950) (pages 177, 378).

JULIUS GREENWALD, Primary Examiner. 

1. A NOVEL ANTI-CAKING AGENT FOR PREVENTING THE CAKING TENDENCY OF NITROGEN-CONTAINING COMPOUNDS, SAID AGENT CONSISTING ESSENTIALLY OF AN ADMIXTURE OF KAOLIN INTO WHICH HAS BEEN INCORPORATED AN ALKALI METAL SALT OF AN ALKYLARYL SULFONIC ACID, SAID SALT BEING PRESENT IN THE AMOUNT OF FROM 0.25 TO 12 WEIGHT PERCENT, BASED ON THE TOTAL WEIGHT OF THE ANTI-CAKING AGENT, AND HAVING A TOTAL OF 7-30 CARBON ATOMS PR MOLECULE WHEREIN THE ARYL PORTION OF SAID MOLECULE IS SELECTED FROM THE GROUP CONSISTING OF BENZENE AND NAPHTHALENE. 